E.s.r. spectra are described for a variety of radicals obtained from the reactions of α-D-glucose, β-D-glucose, and some related substrates with the hydroxyl radical (generated from the TiIII–H2O2 reaction in a flow system). Evidence is presented that attack of ˙OH is largely unselective; for both glucose anomers, all six radicals which can be formed via C–H abstraction are identified. A study has also been made of the relative ease with which these αβ-dioxygen-substituted radicals undergo acid-catalysed fragmentation; this appears to be governed not only by the nature of the leaving group (OH–, OR–) but also by the geometry of the radical (in particular, an axial β-OH group is much more readily lost than an equatorial group). Potential routes for carbohydrate degradation via glycosidic cleavage of first-formed radicals have been identified.
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Gilbert et al. (1981) studied this question.